This invention relates to a method for processing light-sensitive silver halide color photographic material. More particularly, it pertains to a method for processing light-sensitive silver halide color photographic material (hereinafter called "light-sensitive material") which has rapid desilverization characteristic and stabilities of cyan dye image and magenta dye image, and prevents cyan stain and drying contamination in rapid processing.
Generally speaking, for obtaining a color image by processing of a light-sensitive material subjected to imagewise exposure, the metallic silver formed after the color developing step is processed with a processing solution having bleaching ability, and subsequently the processing steps such as water washing, stabilizing substituted for water washing, stabilizing, etc. are provided.
As the processing solution having bleaching ability, bleaching solution, bleach-fixing solution have been known. When a bleaching solution is employed, subsequent to the bleaching step is ordinarily added the step of fixing the silver halide with the fixing agent, but bleaching and fixing are performed in one step with a bleach-fixing solution.
In the processing solution having bleach-fixing ability in the processing of light-sensitive material, as the oxidizing agent for bleaching image silver, inorganic oxidizing agents such as red prussiate, bichromate, etc. have been widely employed.
However, the processing solution having bleaching ability containing these inorganic oxidizing agents has been pointed out to have some vital defects. For example, although red prussiate and bichromate are comparatively excellent in the point of bleaching power of image silver, they may be decomposed with light to form cyan ions or hexavalent chromium ions harmful to human body, thus having undesirable properties in prevention of pollution. Also, since these oxidizing agents have extremely strong oxidizing power, a silver halide solubilizing agent (fixing agent) such as thiosulfate, etc. can be permitted to co-exist in the same processing solution with difficulty, and it is almost impossible to use these oxidizing agents in the bleach-fixing bath, whereby the object of making the processing rapid and simple can be accomplished with difficulty. Further, there is involved a problem that the processing solutions containing these inorganic oxidizing agents are difficult to regenerate and use without disposing these waste solutions after processing.
In contrast, as the solution meeting the demand of making processing rapid, simple, capable of regeneration and use of waste solution, etc. without less problems in pollution, processing solution with a metal complex of an organic acid such as aminopolycarboxylic acid metal complex, etc. as the oxidizing agent is becoming to be used. However, since the processing solution by use of a metal complex of organic acid has slow oxidizing power, it has the drawback that the bleaching speed (oxidizing speed) of image silver (metallic silver) formed in the developing step is slow. For example, ethylenediaminetetraacetic acid iron (III) complex which is considered to have strong bleaching power among organic acid metal complexes is partially used for bleaching solution, and bleach-fixing for a color paper by use of a silver chlorobromide emulsion in combination with a thiosulfate which is the bleach-fixing agent, but it is deficient in bleaching power in high sensitivity light-sensitive material composed mainly of silver bromide, silver iodobromide emulsion, particularly color negative film and color reversal film for photographing containing 0.5 mole % or more of silver iodide as the silver halide, whereby image silver to the extent of trace will remain even when processed for a long time to make desilverization characteristic bad. This tendency particularly remarkably reveals in the bleach-fixing solution coexisting an oxidizing agent as well as in thiosulfate and sulfite since oxidation-reduction potential becomes low.
On the other hand, as a means for accelerating speed of desilverization step, there has bee known a bleach-fixing solution containing an aminopolycarboxylic acid ferric complex salt with thiosulfate in one solution as disclosed in West German Patent No. 866,605. However, when the aminopolycarboxylic ferric complex salt which is originally weak in oxidizing power (bleaching power) is to coexist with a thiosulfate having a reducing power, its bleaching power becomes remarkably weak whereby it is extremely difficult to sufficiently desilver a color photographic material for photographying having high sensitivity and high silver content and thus it cannot be practically used.
Whereas, the demand of rapid processing is not limited to bleach-fixing processing, but the same discussion is applicable to water washing or stabilizing processing up to drying after bleach-fixing. Particularly, in the case of performing stabilizing processing substituted for water washing after the bleach-fixing containing the above organic acid metal complex, it has been found that drying contamination occurs with accompaniment of rapid processing of said stabilizing processing substituted for water washing.
Concerning the technique about the above desilverization characteristic, there has been also proposed the method in which two or three or more bleach-fixing baths are employed. For example, Japanese Provisional Patent Publication No. 11131/1984 (which corresponds to West German Patent Publication No. OLS 22 17 570) discloses a method for processing with a continuous bleach-fixing bath comprising two or more baths, wherein the regenerated solution for bleach-fixing is supplemented according to the counter-current system. According to this method, although there is the advantage that the waste solution amount of the bleach-fixing solution can be made smaller, etc., the regenerated solution has higher photographic material as compared with ordinary supplemental solution, and therefore, particularly when a color light-sensitive material with high iodine content is processed, desilverization cannot be sufficiently effected, and particularly when combined with the rapid processing of stabilizing processing substituted for water washing, there is involved the problem that drying contamination will occur.
On the other hand, Japanese Provisional Patent Publication No. 105148/1983 discloses a method in which at least two bleach-fixing baths are provided, a fixing component is primarily supplemented to the bleach-fixing bath nearer to the color developing bath, and a bleaching component is primarily supplemented to the bleach-fixing bath nearer to the water washing bath, respectively, and processing is conducted according to the counter-current system to improve desilverization characteristic. However, even in this method, desilverization characteristic is not sufficient, and particularly when combined with the rapid processing of stabilizing processing substituted for water washing, there ensues the problem that drying contamination occurs.
In Japanese Provisional Patent Publication No. 75352/1986, there is disclosed a method in which a bleaching agent is supplemented to the bath nearer to the color developing bath and a fixing agent to the bath nearer to the water washing bath, and processing is performed according to the counter-current system to improve this desilverization characteristic. However, although this method is effective to some extent for the purpose of preventing color restration badness, it is insufficient in the point of desilverization characteristic, and particularly when combined with the rapid processing of stabilizing processing substituted for water washing, there is the problem that drying contamination occurs.
Further, in Japanese Provisional Patent Publication No.
91951/1987, it is described that desilverization can be effected within a short time by using two bleach-fixing baths, making the redox potential in the first bath higher than that in the second bath and also making the redox potential in the second bath in the range of +60 mV to -60 mV. However, in this method, although desilverization characteristic is sufficiently good when the bleach-fixing bath contains fresh solution, it can be found that accompanying running thereof or a processing amount, problems of color reproducibility of cyan, occurrence of magenta stain and desilverization are caused, particularly when combined with the rapid processing of stabilizing processing substituted for water washing, there is the problem that drying contamination occurs.